JP2003264327A - Device using polythiofen - Google Patents
Device using polythiofenInfo
- Publication number
- JP2003264327A JP2003264327A JP2003006210A JP2003006210A JP2003264327A JP 2003264327 A JP2003264327 A JP 2003264327A JP 2003006210 A JP2003006210 A JP 2003006210A JP 2003006210 A JP2003006210 A JP 2003006210A JP 2003264327 A JP2003264327 A JP 2003264327A
- Authority
- JP
- Japan
- Prior art keywords
- electronic device
- thin film
- film transistor
- polythiophene
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004065 semiconductor Substances 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 229920000123 polythiophene Polymers 0.000 claims description 85
- 239000010409 thin film Substances 0.000 claims description 49
- -1 oligoarylene Chemical group 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 10
- 125000000732 arylene group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000005556 thienylene group Chemical group 0.000 claims description 8
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 6
- 125000005567 fluorenylene group Chemical group 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 238000005227 gel permeation chromatography Methods 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000005560 phenanthrenylene group Chemical group 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 58
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000004528 spin coating Methods 0.000 description 8
- 229920001940 conductive polymer Polymers 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000976 ink Substances 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 4
- YNZKCHBXBASBJT-UHFFFAOYSA-N 3,4-dioctyl-2,5-dithiophen-2-ylthiophene Chemical compound CCCCCCCCC=1C(CCCCCCCC)=C(C=2SC=CC=2)SC=1C1=CC=CS1 YNZKCHBXBASBJT-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000004377 microelectronic Methods 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- BNXJIUWYGDXAOL-UHFFFAOYSA-N 2,5-bis(5-bromothiophen-2-yl)-3,4-dioctylthiophene Chemical compound CCCCCCCCC=1C(CCCCCCCC)=C(C=2SC(Br)=CC=2)SC=1C1=CC=C(Br)S1 BNXJIUWYGDXAOL-UHFFFAOYSA-N 0.000 description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 3
- WAOUDPOLPWAIGN-UHFFFAOYSA-N 3,4-dioctylthiophene Chemical compound CCCCCCCCC1=CSC=C1CCCCCCCC WAOUDPOLPWAIGN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000010129 solution processing Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- HTYVENFRAWYMAH-UHFFFAOYSA-N 2,5-dibromo-3,4-dioctylthiophene Chemical compound CCCCCCCCC1=C(Br)SC(Br)=C1CCCCCCCC HTYVENFRAWYMAH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 2
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
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- 238000004809 thin layer chromatography Methods 0.000 description 2
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- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- IOOQQIVFCFWSIU-UHFFFAOYSA-M magnesium;octane;bromide Chemical compound [Mg+2].[Br-].CCCCCCC[CH2-] IOOQQIVFCFWSIU-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/464—Lateral top-gate IGFETs comprising only a single gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Thin Film Transistor (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は一般的に、有機超小
形電子デバイスに関し、より詳細には、実施の形態にお
いて、薄膜トランジスタの活物質としてのポリチオフェ
ン類の使用に関する。FIELD OF THE INVENTION This invention relates generally to organic microelectronic devices, and more particularly, in embodiments, to the use of polythiophenes as active materials in thin film transistors.
【０００２】[0002]
【従来の技術】薄膜トランジスタ（ＴＦＴ）の活性半導
体材料として有用な、ある種のポリチオフェン類などの
半導体ポリマーが報告されている。これらのポリマーの
多くは有機溶媒に適度に良好な溶解度を持つため、例え
ば、スピンコーティング、溶液キャスティング、浸漬塗
布、スクリーン印刷、スタンプ印刷、ジェット印刷等の
溶液処理によってＴＦＴ内の半導体チャネル層に加工す
ることができる。通常の溶液処理によって加工できるこ
とは、水素化アモルファスシリコンＴＦＴなどのシリコ
ンベースのデバイスに特有のコストの高い従来のフォト
リソグラフ処理に比べ、その製造をより簡単かつ低コス
トにする。更に、ポリマーＴＦＴと呼ばれる、優れた機
械的耐久性と構造可撓性とを備えた、ポリチオフェン類
などのポリマー材料から作られたトランジスタが望まれ
ている。プラスチック基板上の可撓性ＴＦＴの製造のた
めには、優れた機械的耐久性と構造可撓性が非常に望ま
しい。可撓性ＴＦＴは、構造可撓性と機械的耐久性の特
性を通常必要とする電子的デバイスの設計を可能にする
と考えられる。有機又はポリマートランジスタ要素と共
にプラスチック基板を用いれば、従来の堅牢なシリコン
ＴＦＴを、機械的により頑丈で、構造可撓性のポリマー
ＴＦＴ設計に代えることができる。後者は、大面積画像
センサ、電子ペーパー、その他可撓性ＴＦＴとしての表
示媒体などの大面積デバイスを、小型で構造可撓性の設
計とすることが可能になる点で特に興味深い。また、ス
マートカードや無線周波データキャリア（ＲＦＩＤ）タ
グなどの低価格のマイクロエレクトロニクス用集積回路
論理素子や、メモリ／記憶デバイスにポリマーＴＦＴを
用いると、その機械的耐久性が著しく向上し、その使用
可能寿命が長くなる。2. Description of the Related Art Certain semiconductor polymers such as polythiophenes have been reported to be useful as active semiconductor materials for thin film transistors (TFTs). Many of these polymers have moderately good solubilities in organic solvents, so they can be processed into semiconductor channel layers in TFTs by solution processing such as spin coating, solution casting, dip coating, screen printing, stamp printing, jet printing, etc. can do. Being able to be processed by conventional solution processing makes it easier and cheaper to manufacture compared to the costly conventional photolithographic processing typical of silicon-based devices such as hydrogenated amorphous silicon TFTs. Further, there is a demand for a transistor called a polymer TFT, which is made of a polymer material such as polythiophene and has excellent mechanical durability and structural flexibility. Excellent mechanical durability and structural flexibility are highly desirable for the manufacture of flexible TFTs on plastic substrates. Flexible TFTs are believed to enable the design of electronic devices that typically require structural flexibility and mechanical durability properties. The use of plastic substrates with organic or polymer transistor elements can replace traditional robust silicon TFTs with mechanically more robust, structurally flexible polymer TFT designs. The latter is of particular interest because it allows large area devices such as large area image sensors, electronic paper, and other display media as flexible TFTs to be designed in a small and structurally flexible manner. Further, when polymer TFTs are used for low-cost integrated circuit logic elements for microelectronics such as smart cards and radio frequency data carrier (RFID) tags, and memory / storage devices, their mechanical durability is significantly improved and their use is improved. The usable life is extended.
【０００３】[0003]
【特許文献１】米国特許６，１５０，１９１号[Patent Document 1] US Pat. No. 6,150,191
【特許文献２】米国特許６，１０７，１１７号[Patent Document 2] US Pat. No. 6,107,117
【特許文献３】米国特許５，９６９，３７６号[Patent Document 3] US Pat. No. 5,969,376
【特許文献４】米国特許５，６１９，３５７号[Patent Document 4] US Pat. No. 5,619,357
【特許文献５】米国特許５，７７７，０７０号[Patent Document 5] US Pat. No. 5,777,070
【０００４】[0004]
【発明が解決しようとする課題】しかし、半導体ポリチ
オフェン類の多くは、周囲の酸素によって酸化的にドー
プされ、導電率が増大するため、空気に触れると安定で
はない。この結果、これらの材料から製造したデバイス
ではオフ電流が大きくなり、このため電流オン／オフ比
が小さくなってしまう。従ってこれらの材料の多くは、
材料加工とデバイス製造の際には環境酸素を排除して酸
化的ドーピングを防止するよう厳重な対策を講じなけれ
ばならない。この予防策は製造コストを押し上げるた
め、特に大面積デバイスのための、アモルファスシリコ
ン技術に代わる経済的な技術としてのある種のポリマー
ＴＦＴの魅力が削がれてしまう。これら及びその他の欠
点は、本発明の実施の形態において回避され、あるいは
最小となる。However, many of the semiconductor polythiophenes are not stable when exposed to air because they are oxidatively doped with ambient oxygen and have increased conductivity. As a result, the devices manufactured from these materials have a large off current, which reduces the current on / off ratio. Therefore, many of these materials
Strict measures must be taken during material processing and device manufacturing to exclude environmental oxygen and prevent oxidative doping. This precaution adds to the manufacturing cost and detracts from the appeal of certain polymer TFTs as an economical alternative to amorphous silicon technology, especially for large area devices. These and other drawbacks are avoided or minimized in embodiments of the present invention.
【０００５】本発明は、上記課題を鑑みてなされたもの
であり、薄膜トランジスタデバイスのような超小形電子
デバイスの用途に有用な、ポリチオフェン類などの半導
体ポリマーの提供を目的とする。The present invention has been made in view of the above problems, and an object of the present invention is to provide a semiconductor polymer such as polythiophene, which is useful for use in a microelectronic device such as a thin film transistor device.
【０００６】[0006]
【課題を解決するための手段】本発明の態様は次のとお
りである。下記化３の構造式（Ｉ）を持つポリチオフェ
ンを含む電子的デバイス。The aspects of the present invention are as follows. An electronic device comprising polythiophene having the structural formula (I) as shown below.
【０００７】[0007]
【化３】
式中、Ｒ及びＲ’は側鎖であり、Ａは二価結合基であ
り、ｘ及びｙは非置換チエニレン単位の数を示し、ｚは
０又は１であり、ｘとｙとの和は０より大きく、ｍはセ
グメントの数を示し、ｎは重合度を示す。;Ｒ及びＲ’
はそれぞれ独立して、アルキル及び置換アルキルより選
ばれ、Ａはアリーレンである電子的デバイス。；Ｒ及び
Ｒ’は約３〜約２０の炭素原子を含むデバイス。；Ｒ及
びＲ’はそれぞれ独立して、アルキルとアルキル誘導体
とから成る群より選ばれるものであって、アルキル誘導
体は、アルコキシアルキル、シロキシ置換アルキル、パ
ーフルオロアルキルであるパーハロアルキル、及びポリ
エーテルであり、Ａは、フェニレン、ビフェニレン、フ
ェナントレニレン、ジヒドロフェナントレニレン、フル
オレニレン、オリゴアリーレン、メチレン、ポリメチレ
ン、ジアルキルメチレン、ジオキシアルキレン、ジオキ
シアリーレン、及びオリゴエチレンオキシドである、ア
リーレンから成る群より選ばれる電子的デバイス。；Ｒ
及びＲ’はそれぞれ独立してプロピル、ブチル、ペンチ
ル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、
ウンデシル、ドデシル、トリデシル、テトラデシル、ペ
ンタデシル、及びそれらの異性体から成る群より選ばれ
るデバイス。；Ａは、炭素数約６〜約４０のアリーレン
であるデバイス。；Ｒ及びＲ’は、ヘキシル、ヘプチ
ル、オクチル、ノニル、デシル、ウンデシル、ドデシ
ル、トリデシル、テトラデシル、及びペンタデシルから
成る群より選ばれ、Ａは、フェニレン、ビフェニレン、
及びフルオレニレンから成る群より選ばれ、ｘ及びｙは
それぞれ独立して０〜約１０の数であり、ｍは１〜約５
の数であるデバイス。；ｎは約７〜約５，０００であ
り、いずれもポリスチレン標準を用いたゲル浸透クロマ
トグラフ法より求めた、ポリチオフェンの数平均分子量
（Ｍn）は約２，０００〜約１０万であり、重量平均分
子量（Ｍw）は約４，０００〜約５０万である電子的デ
バイス。；基板と、ゲート電極と、ゲート誘電体層と、
ソース電極及びドレイン電極と、ソース及びドレイン電
極とゲート誘電体層とに接した半導体層と、を含み、半
導体層はポリチオフェンを含む薄膜トランジスタ。；Ｒ
及びＲ’はそれぞれ独立して、アルキル、アルコキシア
ルキル、シロキシ置換アルキル、及びパーハロアルキル
から成る群より選ばれ、Ａは、フェニレン、ビフェニレ
ン、フェナントレニレン、ジヒドロフェナントレニレ
ン、フルオレニレン、オリゴアリーレン、メチレン、ポ
リメチレン、ジアルキルメチレン、ジオキシアルキレ
ン、ジオキシアリーレン、及びオリゴエチレンオキシド
から成る群より選ばれる薄膜トランジスタデバイス。；
ｎは約５〜約５，０００であり、いずれもポリスチレン
標準を用いたゲル浸透クロマトグラフ法より求めた、ポ
リチオフェンの数平均分子量（Ｍn）は約４，０００〜
約５万であり、重量平均分子量（Ｍw）は約５，０００
〜約１０万である薄膜トランジスタデバイス。；Ｒ及び
Ｒ’は約３〜約２０の炭素原子を含むアルキルである薄
膜トランジスタデバイス。；Ａは炭素数約６〜約３０の
アリーレンである薄膜トランジスタデバイス。；Ａは炭
素数約６〜約２４のアリーレンである薄膜トランジスタ
デバイス。；Ａは、フェニレン、ビフェニレン、又はフ
ルオレニレンである薄膜トランジスタデバイス。；保護
層を備えた薄膜トランジスタデバイス。；ポリチオフェ
ンは、下記化４の構造式（１）〜（１４）を持つポリチ
オフェン類から成る群より選ばれるデバイス。[Chemical 3] In the formula, R and R ′ are side chains, A is a divalent bonding group, x and y represent the number of unsubstituted thienylene units, z is 0 or 1, and the sum of x and y is Greater than 0, m indicates the number of segments, and n indicates the degree of polymerization. R and R '
Are each independently selected from alkyl and substituted alkyl, and A is arylene. R and R'is a device containing from about 3 to about 20 carbon atoms. R and R'are each independently selected from the group consisting of alkyl and alkyl derivatives, wherein the alkyl derivative is alkoxyalkyl, siloxy substituted alkyl, perhaloalkyl which is perfluoroalkyl, and polyether. Where A is phenylene, biphenylene, phenanthrenylene, dihydrophenanthrenylene, fluorenylene, oligoarylene, methylene, polymethylene, dialkylmethylene, dioxyalkylene, dioxyarylene, and oligoethylene oxide, the group consisting of arylene. Electronic device of choice. ; R
And R ′ are each independently propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
A device selected from the group consisting of undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and their isomers. A is a device in which A is arylene having about 6 to about 40 carbon atoms. R and R'are selected from the group consisting of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl; A is phenylene, biphenylene,
And fluorenylene, x and y are each independently a number from 0 to about 10, and m is 1 to about 5
The number of devices. N is about 7 to about 5,000, and the number average molecular weight (M n ) of polythiophene is about 2,000 to about 100,000, which is determined by gel permeation chromatography using a polystyrene standard. An electronic device having a weight average molecular weight (M w ) of about 4,000 to about 500,000. A substrate, a gate electrode, a gate dielectric layer,
A thin film transistor including a source electrode and a drain electrode, and a semiconductor layer in contact with the source and drain electrodes and a gate dielectric layer, the semiconductor layer including polythiophene. ; R
And R ′ are each independently selected from the group consisting of alkyl, alkoxyalkyl, siloxy substituted alkyl, and perhaloalkyl, A is phenylene, biphenylene, phenanthrenylene, dihydrophenanthrenylene, fluorenylene, oligoarylene. , A methylene, polymethylene, dialkylmethylene, dioxyalkylene, dioxyarylene, and oligoethylene oxide thin film transistor device. ;
n is about 5 to about 5,000, and the number average molecular weight (M n ) of polythiophene determined by gel permeation chromatography using polystyrene standards is about 4,000 to about 4,000.
It is about 50,000, and the weight average molecular weight (M w ) is about 5,000.
A thin film transistor device that is about 100,000. A thin film transistor device, wherein R and R ′ are alkyl containing from about 3 to about 20 carbon atoms. A thin film transistor device wherein A is arylene having from about 6 to about 30 carbon atoms. A thin film transistor device, wherein A is arylene having from about 6 to about 24 carbon atoms. A is a thin film transistor device, wherein A is phenylene, biphenylene, or fluorenylene. A thin film transistor device with a protective layer. The polythiophene is a device selected from the group consisting of polythiophenes having structural formulas (1) to (14) shown below.
【０００８】[0008]
【化４】
；ｎは約５〜約５，０００であるデバイス。；ｎは約１
０〜約１，０００であるデバイス。；Ｍnは約４，００
０〜約５万、Ｍwは約５，０００〜約１０万であるデバ
イス。；ポリチオフェンは、下記化５の構造式（１）〜
（８）を持つポリチオフェン類から成る群より選ばれる
デバイス。[Chemical 4] A device wherein n is from about 5 to about 5,000. ; N is about 1
Devices that are 0 to about 1,000. Mn is about 4,000
A device having 0 to about 50,000 and M w of about 5,000 to about 100,000. Polythiophene is represented by the following structural formula (1)
A device selected from the group consisting of polythiophenes having (8).
【０００９】[0009]
【化５】
；ポリチオフェンは、下記化６の構造式（１）〜（１
４）を持つポリチオフェン類から成る群より選ばれる薄
膜トランジスタデバイス。[Chemical 5] The polythiophene has the following structural formulas (1) to (1)
A thin film transistor device selected from the group consisting of polythiophenes having 4).
【００１０】[0010]
【化６】
；ポリチオフェンは、下記化７の構造式（１）〜（８）
を持ち、必要に応じて、式中、ｎは約５〜約５，０００
であるポリチオフェン類から成る群より選ばれる薄膜ト
ランジスタデバイス。[Chemical 6] Polythiophene is represented by the following structural formulas (1) to (8).
And, where necessary, n is from about 5 to about 5,000.
Is a thin film transistor device selected from the group consisting of polythiophenes.
【００１１】[0011]
【化７】
；ｘ、ｙ、及びｍは１〜３であり、ｚは０又は１であ
り、デバイスは薄膜トランジスタであるデバイス。；
ｘ、ｙ、及びｍは１であり、ｚは０又は１であり、デバ
イスは薄膜トランジスタであるデバイス。；ｘ、ｙ、及
びｍは１であり、ｚは０又は１であり、あるいは、ｘ、
ｙ、及びｍは１であり、ｚは０であり、デバイスは薄膜
トランジスタであるデバイス。；基板は、ポリエステ
ル、ポリカーボネート、又はポリイミドであるプラスチ
ックシートであり、ゲート、ソース、及びドレイン電極
は、金、ニッケル、アルミニウム、プラチナ、酸化イン
ジウムチタン、又は導電性ポリマーを含み、ゲート誘電
体層は、窒化ケイ素、酸化ケイ素、又は絶縁性ポリマー
を含むものである薄膜トランジスタデバイス。；基板
は、ガラス又はプラスチックシートであり、ゲート、ソ
ース、及びドレイン電極はそれぞれ金を含み、ゲート誘
電体層は、ポリ（メタクリレート）、ポリ（ビニルフェ
ノール）である有機ポリマーを含むものである薄膜トラ
ンジスタデバイス。；ゲート、ソース、及びドレイン電
極は、ポリスチレンスルホナートをドープしたポリ
（３，４−エチレンジオキシチオフェン）であるドープ
した有機導電性ポリマー、あるいは、ポリマーバインダ
中にコロイド状に分散した銀を含む導電性インキ／ペー
ストから製造され、ゲート誘電体層は、有機ポリマー又
は無機酸化物粒子−ポリマー複合材である薄膜トランジ
スタデバイス。；下記化８に包含されるポリチオフェン
類。[Chemical 7] A device in which x, y, and m are 1 to 3, z is 0 or 1, and the device is a thin film transistor. ;
The device wherein x, y, and m are 1, z is 0 or 1, and the device is a thin film transistor. X, y, and m are 1 and z is 0 or 1, or x,
The device in which y and m are 1, z is 0, and the device is a thin film transistor. The substrate is a plastic sheet that is polyester, polycarbonate, or polyimide, the gate, source, and drain electrodes include gold, nickel, aluminum, platinum, indium titanium oxide, or a conductive polymer, and the gate dielectric layer is , A silicon nitride, a silicon oxide, or an insulating polymer. The substrate is a glass or plastic sheet, the gate, source, and drain electrodes each comprise gold, and the gate dielectric layer comprises an organic polymer that is poly (methacrylate), poly (vinylphenol). The gate, source, and drain electrodes comprise a doped organic conductive polymer, which is poly (3,4-ethylenedioxythiophene) doped with polystyrene sulfonate, or colloidally dispersed silver in a polymer binder. A thin film transistor device manufactured from a conductive ink / paste, wherein the gate dielectric layer is an organic polymer or inorganic oxide particle-polymer composite. Polythiophenes included in the following chemical formula 8.
【００１２】[0012]
【化８】
式中、Ｒ及びＲ’は側鎖であって、それぞれ独立して例
えば、アルキル及びアルキル誘導体から成る群より選ば
れ、アルキル誘導体は、アルコキシアルキル、シロキシ
置換アルキル、パーフルオロアルキルなどのパーハロア
ルキル、オリゴエチレンオキシドなどのポリエーテル、
ポリシロキシ、等であり、Ａは二価結合基であって、例
えば、フェニレン、ビフェニレン、フェナントレニレ
ン、ジヒドロフェナントレニレン、フルオレニレン、オ
リゴアリーレン、メチレン、ポリメチレン、ジアルキル
メチレン、ジオキシアルキレン、ジオキシアリーレン、
及びオリゴエチレンオキシド、等のアリーレンから成る
群より選ばれ、ｘ及びｙはそれぞれ独立して０〜１０よ
り選ばれる整数であり、ｚは０又は１のいずれかであ
り、ｘとｙとの和は０より大きく、ｍは１〜約５の整数
であり、ｎは重合度であって、通常、約５〜５，０００
以上、より詳細には約１０〜約１，０００とすることが
できる。いずれもポリスチレン標準を用いたゲル浸透ク
ロマトグラフ法より求めた、ポリチオフェン類の数平均
分子量（Ｍn）は、例えば約２，０００〜約１０万、よ
り詳細には約４，０００〜約５万とすることができ、そ
の重量平均分子量（Ｍw）は約４，０００〜約５０万、
より詳細には約５，０００〜約１０万とすることができ
る。[Chemical 8] In the formula, R and R ′ are side chains and are independently selected from the group consisting of, for example, alkyl and alkyl derivatives, and the alkyl derivative is peroxyalkyl such as alkoxyalkyl, siloxy-substituted alkyl, or perfluoroalkyl, Polyether such as oligoethylene oxide,
Polysiloxy, etc., A is a divalent linking group, for example, phenylene, biphenylene, phenanthrenylene, dihydrophenanthrenylene, fluorenylene, oligoarylene, methylene, polymethylene, dialkylmethylene, dioxyalkylene, dialkyl. Oxyarylene,
And an arylene such as oligoethylene oxide, x and y are each independently an integer selected from 0 to 10, z is either 0 or 1, and the sum of x and y is Greater than 0, m is an integer from 1 to about 5, n is the degree of polymerization, usually about 5 to 5,000.
More specifically, it can be about 10 to about 1,000. The number average molecular weight (M n ) of the polythiophenes, which is determined by gel permeation chromatography using polystyrene standards, is about 2,000 to about 100,000, more specifically about 4,000 to about 50,000. And its weight average molecular weight (M w ) is about 4,000 to about 500,000,
More specifically, it can be about 5,000 to about 100,000.
【００１３】側鎖Ｒ及びＲ’の例としては、例えば炭素
数約１〜約２５、より詳細には約４〜約１２の、ブチ
ル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニ
ル、デシル、ウンデシル、ドデシル、それらの異性体、
等のアルキル、炭素数１〜約２５の、例えば、メトキシ
プロピル、メトキシブチル、メトキシヘキシル、メトキ
シヘプチル、等のアルコキシアルキル、ポリエチレンオ
キシドなどのポリエーテル鎖、パーフルオロアルキル
（例えば、ノナフルオロヘキシル、ノナフルオロヘプチ
ル、ペンタデカフルオロオクチル、トリデカフルオロノ
ニル、等）などのパーハロアルキル、トリアルキルシロ
キシアルキル等のポリシロキシ鎖などが挙げられる。Examples of the side chains R and R'include, for example, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl having about 1 to about 25 carbon atoms, more specifically about 4 to about 12 carbon atoms, Dodecyl, their isomers,
Etc., alkyl having 1 to about 25 carbon atoms, for example, alkoxyalkyl such as methoxypropyl, methoxybutyl, methoxyhexyl, methoxyheptyl, polyether chains such as polyethylene oxide, perfluoroalkyl (eg, nonafluorohexyl, nona Fluoroheptyl, pentadecafluorooctyl, tridecafluorononyl, etc.) and polysiloxy chains such as trialkylsiloxyalkyl.
【００１４】使用されるポリチオフェン類は、繰り返し
チエニレン単位を含むことができ、その中では特定のチ
エニレンだけが側鎖を持ち、またチエニレン単位はポリ
チオフェン主鎖上に位置規則性（レジオレギュラ：regi
oregular）に配列している。The polythiophenes used can contain repeating thienylene units, of which only certain thienylene units have side chains, and thienylene units are also regioregular (regiregular) on the polythiophene backbone.
oregular).
【００１５】このポリチオフェン類は実施の形態におい
て実質的に安定であり、周囲条件でこれを用いたデバイ
スの製造が可能である。またそのデバイスは高い電流オ
ン／オフ比を持ち、更に操作上より安定で、その性能は
通常、位置規則性ポリ（３−アルキルチオフェン−２，
５−ジイル）などの公知の位置規則性ポリチオフェン類
から製造したもののように急激に低下することがない。
より詳細には、本発明のポリチオフェン類は実施の形態
において、非置換の２,５−チエニレン単位と、必要に
応じて二価結合基とに挾まれた、３，４−二置換−２，
５−チエニレン単位の繰り返しセグメントを含む。側鎖
は、薄膜製造の際にポリチオフェン類の分子自己組織化
の誘発及び促進を促す。多少の回転自由度を持つ非置換
チエニレン単位と必要に応じた二価結合基は、ポリチオ
フェン鎖に沿って伸びるπ共役を妨げ、その酸化的ドー
ピング傾向を抑制することができる。The polythiophenes are substantially stable in the embodiment, and devices using the polythiophenes can be manufactured under ambient conditions. The device also has a high current on / off ratio, is more stable in operation, and its performance is usually regioregular poly (3-alkylthiophene-2,
It does not drop sharply as in the case of those prepared from known regioregular polythiophenes such as 5-diyl).
More specifically, the polythiophenes of the present invention include, in embodiments, 3,4-disubstituted-2,2, which is sandwiched between an unsubstituted 2,5-thienylene unit and optionally a divalent linking group.
It contains repeating segments of 5-thienylene units. The side chains facilitate the induction and promotion of molecular self-assembly of polythiophenes during thin film fabrication. An unsubstituted thienylene unit having some rotational freedom and optionally a divalent linking group can prevent π conjugation extending along the polythiophene chain and suppress its oxidative doping tendency.
【００１６】本発明は、上記特徴により、薄膜トランジ
スタデバイスのような超小形電子デバイスの用途に有用
な、ポリチオフェン類などの半導体ポリマーの提供する
ことができる。According to the above characteristics, the present invention can provide a semiconductor polymer such as polythiophene, which is useful for use in a microelectronic device such as a thin film transistor device.
【００１７】また、本発明は、その薄膜の吸収スペクト
ルから求めたバンドギャップが約１．５〜約３ｅＶであ
るポリチオフェン類の提供であり、このポリチオフェン
類は、薄膜トランジスタ半導体チャネル層材料としての
使用に適する。The present invention also provides polythiophenes having a bandgap of about 1.5 to about 3 eV determined from the absorption spectrum of the thin film, which polythiophene is suitable for use as a thin film transistor semiconductor channel layer material. Suitable.
【００１８】更に本発明は、超小形電子部品として有用
なポリチオフェン類の提供であり、このポリチオフェン
類は、ジクロロメタン、テトラヒドロフラン、トルエ
ン、キシレン、メシチレン、クロロベンゼン等の一般的
な有機溶媒に適度な、例えば約０.１重量％以上の溶解
度を持ち、このためスピンコーティング、スクリーン印
刷、スタンプ印刷、浸漬塗布、溶液キャスティング、ジ
ェット印刷等の溶液処理によって経済的に加工すること
ができる。The present invention further provides polythiophenes useful as microminiature electronic components, which are suitable for general organic solvents such as dichloromethane, tetrahydrofuran, toluene, xylene, mesitylene, chlorobenzene, etc. It has a solubility of about 0.1% by weight or more, and therefore can be economically processed by solution processing such as spin coating, screen printing, stamp printing, dip coating, solution casting, jet printing.
【００１９】別の本発明の特徴は、ポリチオフェンチャ
ネル層を持ち、その層の導電率が１０-6〜約１０-9Ｓ／
ｃｍ（ジーメンス／センチメートル）である薄膜トラン
ジスタなどの電子的デバイスの提供である。Another feature of the invention is that it has a polythiophene channel layer having a conductivity of 10 -6 to about 10 -9 S /.
The provision of electronic devices such as thin film transistors that are cm (Siemens / centimeter).
【００２０】また更に本発明の特徴は、ポリチオフェン
類とそれを用いたデバイスの提供であり、このデバイス
は酸素の悪影響に対して優れた抵抗性を示し、つまりこ
のデバイスは比較的高い電流オン／オフ比を示し、その
性能は通常、位置規則性ポリ（３−アルキルチオフェン
−２,５−ジイル）などの位置規則性ポリチオフェン類
から製造したもののように急激に低下することなく、あ
るいは最小限の低下と同程度である。A further feature of the present invention is to provide polythiophenes and devices using the same, which devices exhibit excellent resistance to the adverse effects of oxygen, that is, the devices have relatively high current on / off. It exhibits an off-ratio, and its performance usually does not drop sharply or at a minimum, such as those made from regioregular polythiophenes such as regioregular poly (3-alkylthiophene-2,5-diyl). It is about the same as the decline.
【００２１】また別の本発明の特徴は、特殊な構造的特
徴を持ち、これにより適当な加工条件下において分子が
自己配列し、またその構造的特徴がデバイス性能の安定
性をも向上させるようなポリチオフェン類の提供であ
る。適当な分子配列は、薄膜中により高次の分子構造配
列を形成し、効率良く電荷キャリアを移動させて高い電
気的性能を可能とする。Another feature of the present invention is that it has special structural features that allow the molecules to self-align under appropriate processing conditions, and that the structural features also improve device performance stability. To provide various polythiophenes. A suitable molecular arrangement forms a higher-order molecular structure arrangement in a thin film, and efficiently moves charge carriers to enable high electric performance.
【００２２】[0022]
【発明の実施の形態】より詳細には、ポリチオフェン類
の例は下記化９のものである。More specifically, examples of polythiophenes are shown below.
【００２３】[0023]
【化９】
構造式（Ｉ）を参照するならば、ポリチオフェン類は、
３，４−二置換−２，５−チエニレン単位と、非置換
２，５−チエニレン単位と、必要に応じて二価の結合基
との位置規則性セグメントを含むものである。ポリチオ
フェン（Ｉ）（構造式（１）〜（１４）を参照）中の側
鎖の位置規則性は、適当な加工条件下で薄膜を製造する
際に分子の自己配列を誘導し、薄膜中に高度に組織化さ
れた微細構造を作ることができると考えられる。薄膜ト
ランジスタの半導体チャネル層中の高次の微細構造はト
ランジスタ性能を向上する。これらのポリチオフェン類
は、適当な溶媒系に溶解した溶液から厚さ約１０〜約５
００ｎｍの薄膜を作ると、強い分子内π−πスタックが
形成され、導電性となって効率良く電荷キャリヤを移動
すると考えられる。（Ｉ）中の非置換チエニレン部分は
多少の回転自由度を持つため、酸化的ドーピングを十分
に抑制する程度に（Ｉ）の分子内に広がるπ共役を妨げ
る。従って、このポリチオフェン類は周囲条件下で安定
であり、これらのポリチオフェン類から製造したデバイ
スは、位置規則性ポリ（３−アルキルチオフェン−２，
５−ジイル）などの位置規則性ポリチオフェン類より機
能的により安定である。保護しなくても、構造式（Ｉ）
のポリチオフェン類から製造したデバイスは、その実施
の形態において、通常数週間から数ヶ月間、例えば約３
〜約１２週間も安定である。これに対し、位置規則性ポ
リ（３−アルキルチオフェン−２，５−ジイル）を用い
たデバイスは、周囲の酸素に曝すと数日で、例えば５日
足らずで劣化してしまう。本願のポリチオフェン類から
製造したデバイスはまた、高い電流オン／オフ比を持
ち、その性能は、材料調製、デバイス製造、及び評価の
際に周囲の酸素を排除するよう厳しい操作上の予防措置
を講じなくても、ポリ（３−アルキルチオフェン−２，
５−ジイル）のものほど急激には変化しない。酸化的ド
ーピングに対して安定な材料は、低コストデバイスの製
造には特に有用である。この材料はより安定であるた
め、通常、厳重に不活性な雰囲気中で取り扱う必要がな
く、故にその製造工程がより単純かつ低コストで、その
工程をシンプルな大規模製造工程とすることができる。[Chemical 9] Referring to Structural Formula (I), the polythiophenes are
It contains a regioregular segment of a 3,4-disubstituted-2,5-thienylene unit, an unsubstituted 2,5-thienylene unit, and optionally a divalent linking group. The regioregularity of side chains in polythiophene (I) (see structural formulas (1) to (14)) induces self-alignment of molecules during the production of a thin film under appropriate processing conditions, and It is believed possible to create highly organized microstructures. Higher order microstructures in the semiconductor channel layer of thin film transistors improve transistor performance. These polythiophenes have a thickness of about 10 to about 5 from a solution dissolved in a suitable solvent system.
It is considered that when a thin film of 00 nm is formed, a strong intramolecular π-π stack is formed, which becomes conductive and efficiently moves charge carriers. Since the unsubstituted thienylene moiety in (I) has some rotational freedom, it interferes with π conjugation spreading in the molecule of (I) to the extent that oxidative doping is sufficiently suppressed. Therefore, the polythiophenes are stable under ambient conditions, and devices made from these polythiophenes show regioregular poly (3-alkylthiophene-2,
It is functionally more stable than regioregular polythiophenes such as 5-diyl). Structural formula (I) without protection
Devices manufactured from the polythiophenes of, for example, are typically for several weeks to several months, for example about 3
~ Stable for about 12 weeks. In contrast, a device using regioregular poly (3-alkylthiophene-2,5-diyl) deteriorates in a few days, for example, in less than 5 days when exposed to ambient oxygen. Devices made from the polythiophenes of the present application also have high current on / off ratios, and their performance takes strict operational precautions to exclude ambient oxygen during material preparation, device fabrication, and evaluation. Even without, poly (3-alkylthiophene-2,
It does not change as rapidly as that of 5-diyl). Materials that are stable to oxidative doping are particularly useful for making low cost devices. Because this material is more stable, it usually does not need to be handled in a severely inert atmosphere, thus making the manufacturing process simpler and less costly, and can be a simple large-scale manufacturing process. .
【００２４】実施の形態においてこのポリチオフェン類
は、一般的な被覆用溶媒に可溶であり、例えば、ジクロ
ロメタン、１，２−ジクロロエタン、テトラヒドロフラ
ン、トルエン、キシレン、メシチレン、クロロベンゼン
等の溶媒に約０．１重量％以上、より詳細には約０．５
〜約１５重量％の溶解度を持つ。更に、このポリチオフ
ェン類を薄膜トランジスタデバイスの半導体チャネル層
に加工すると安定した導電率となり、例えば、一般的な
４プローブ伝導率測定法によれば、約１０-9〜約１０-6
Ｓ／ｃｍ、より詳細には約１０-8〜約１０-7Ｓ／ｃｍで
ある。In the embodiment, the polythiophenes are soluble in common coating solvents, for example, in a solvent such as dichloromethane, 1,2-dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, chlorobenzene, etc. 1% by weight or more, more specifically about 0.5
Has a solubility of about 15% by weight. Further, when the polythiophenes are processed into a semiconductor channel layer of a thin film transistor device, the conductivity becomes stable. For example, according to a general 4-probe conductivity measuring method, about 10 −9 to about 10 −6.
S / cm, more particularly about 10 -8 to about 10 -7 S / cm.
【００２５】本発明のポリチオフェン類は、適切に組み
立てられたモノマー、例えば、トリチオフェンモノマー
の重合により調製可能である。例えば、スキーム１に従
って例示のポリチオフェン類（Ia）及び（Ib）を調製す
るには、２，５−ビス（２−チエニル）−３，４−ジ−
Ｒ−チオフェン（IIａ）、又は２，５−ビス（５−ブロ
モ−２−チエニル）−３，４−ジ−Ｒ−チオフェン（II
b）を用いる。モノマー類（IIa）及び（IIb）はそれぞ
れその中央のチエニレン単位上に２つの側鎖を持つた
め、重合すると側鎖がそれぞれのポリチオフェン主鎖上
に位置規則性に並んだポリチオフェン類(Ia)及び(Ib)と
なる。位置規則性カップリング反応が必要なポリ（３−
アルキルチオフェン−２，５−ジイル）などの位置規則
性ポリチオフェン類の調製とは異なり、本発明のポリチ
オフェン類は、位置規則性の複雑さの無い通常の重合法
により調製できる。詳細には、（Ia）は、ＦｅＣｌ3を
介在させた酸化的カップリング重合によりモノマー (II
a)から、あるいはレイケ（Reike）亜鉛で処理後Ｎｉ
（ｄｐｐｅ）Ｃｌ2触媒を加えることによりモノマー(II
b)から調製できる。一方、ポリチオフェン（Ib)は、適
当なアリーレンジボロナートとのスズキカップリング反
応により(IIb)から容易に得ることができる。The polythiophenes of the present invention can be prepared by the polymerization of properly assembled monomers such as trithiophene monomers. For example, to prepare the exemplary polythiophenes (Ia) and (Ib) according to Scheme 1, 2,5-bis (2-thienyl) -3,4-di-
R-thiophene (IIa) or 2,5-bis (5-bromo-2-thienyl) -3,4-di-R-thiophene (II
Use b). Since the monomers (IIa) and (IIb) each have two side chains on the thienylene unit in the center of the polythiophene main chain, polythiophenes (Ia) and (Ib). Poly (3-) that requires regioregular coupling reaction
Unlike the preparation of regioregular polythiophenes such as alkylthiophene-2,5-diyl), the polythiophenes of the present invention can be prepared by conventional polymerization methods without regioregular complexity. Specifically, (Ia) is a monomer (II) formed by oxidative coupling polymerization mediated by FeCl 3.
a) or after treatment with Reike zinc Ni
By adding a (dppe) Cl 2 catalyst, the monomer (II
It can be prepared from b). On the other hand, polythiophene (Ib) can be easily obtained from (IIb) by Suzuki coupling reaction with a suitable arylenediboronate.
【００２６】[0026]
【化１０】スキーム１
詳細には、（IIa）の重合は、乾燥空気の気流中で、塩
化物溶媒、例えばクロロホルムに溶解した（IIa）の１
モル等量の溶液を、約１〜約５モル当量の無水ＦｅＣｌ
3のクロロホルム懸濁液に加えることにより行うことが
できる。得られた混合物を、乾燥空気気流中、あるいは
乾燥空気の泡をゆっくり反応混合物中に通しながら、約
２５〜約５０℃の温度で、約３０分〜約４８時間反応さ
せる。反応後、反応混合物を水又は希塩酸水溶液で洗
い、希アンモニア水溶液と撹拌した後に水で洗い、次に
メタノール又はアセトンから沈殿させてポリマー生成物
を単離する。レイケ亜鉛法では、無水テトラヒドロフラ
ンに溶解した１０ミリモル当量の（IIｂ）を、１１ミリ
モル当量の調製直後のレイケＺｎの無水テトラヒドロフ
ラン懸濁液に、２０〜４０分かけて良く撹拌しながら滴
下して加え、次に得られた混合物を、室温（約２２〜約
２５℃）で約３０分〜約２時間反応させる。続いて、約
０．１ミリモル当量のＮｉ（ｄｐｐｅ）Ｃｌ2の無水テ
トラヒドロフラン懸濁液を約１０〜約２０分かけてゆっ
くり加え、次に混合物を約４０〜約６５℃で２〜５時間
加熱する。次に反応混合物を、激しくかき混ぜながら希
塩酸−メタノール溶液に注ぎ、ポリマー生成物を沈殿さ
せる。後者を熱テトラヒドロフランに再溶解した後、希
アンモニア−メタノール溶液から再沈殿させる。 Scheme 1 In detail, the polymerization of (IIa) is carried out by dissolving 1 of (IIa) in a chloride solvent such as chloroform in a stream of dry air.
A molar equivalent solution is added to about 1 to about 5 molar equivalents of anhydrous FeCl 2.
It can be carried out by adding 3 to the chloroform suspension. The resulting mixture is reacted at a temperature of about 25 to about 50 ° C. for about 30 minutes to about 48 hours in a stream of dry air or while slowly passing bubbles of dry air through the reaction mixture. After the reaction, the reaction mixture is washed with water or a dilute aqueous hydrochloric acid solution, stirred with a dilute aqueous ammonia solution and then washed with water, and then precipitated from methanol or acetone to isolate the polymer product. In the Reike zinc method, 10 millimolar equivalents of (IIb) dissolved in anhydrous tetrahydrofuran are added dropwise to 11 millimolar equivalents of freshly prepared suspension of Reike Zn in anhydrous tetrahydrofuran over 20 to 40 minutes with good stirring. Then, the obtained mixture is reacted at room temperature (about 22 to about 25 ° C.) for about 30 minutes to about 2 hours. Subsequently, about 0.1 millimolar equivalent of a suspension of Ni (dppe) Cl 2 in anhydrous tetrahydrofuran is slowly added over about 10 to about 20 minutes, and then the mixture is heated at about 40 to about 65 ° C. for 2 to 5 hours. To do. The reaction mixture is then poured into dilute hydrochloric acid-methanol solution with vigorous stirring to precipitate the polymer product. The latter is redissolved in hot tetrahydrofuran and then reprecipitated from dilute ammonia-methanol solution.
【００２７】より詳細には、ポリチオフェン（Ib）は、
モノマー（IIb）と適当なアリーレンジボロナートとの
スズキカップリング反応より得られる。等モル当量のモ
ノマー（IIb）とアリーレンジボロナートとのトルエン
溶液と、約２〜６モル％のテトラキス（トリフェニルホ
スフィン）パラジウムと、１〜２Ｍの水溶液とした約２
〜約４モル等量の炭酸ナトリウムなどの無機塩基と、約
１〜５モル％の、テトラブチルアンモニウム＝クロリド
又はトリカプリリルメチルアンモニウム＝クロリドなど
の相間移動触媒との混合物を、不活性雰囲気中で４８時
間、約９０℃に加熱する。重合後、ポリチオフェン生成
物（Ib）をメタノールから繰り返し沈殿させて単離す
る。More specifically, polythiophene (Ib) is
Obtained by Suzuki coupling reaction of monomer (IIb) with the appropriate arylenediboronate. A toluene solution of equimolar equivalents of monomer (IIb) and arylenediboronate, about 2-6 mol% tetrakis (triphenylphosphine) palladium, and about 2M aqueous solution of about 2
To about 4 mole equivalents of an inorganic base such as sodium carbonate and about 1 to 5 mole% of a phase transfer catalyst such as tetrabutylammonium chloride or tricaprylylmethylammonium chloride in an inert atmosphere. Heat to about 90 ° C. for 48 hours. After polymerization, the polythiophene product (Ib) is isolated by repeated precipitation from methanol.
【００２８】本発明の様々な代表的な実施の形態を図１
〜図４に示す。ここでは薄膜トランジスタ（ＴＦＴ）構
造体中のチャネル材料としてポリチオフェン類を用いて
いる。Various exemplary embodiments of the present invention are shown in FIG.
~ Shown in FIG. Here, polythiophenes are used as the channel material in the thin film transistor (TFT) structure.
【００２９】図１は、基板１６と、それに接した金属接
点１８（ゲート電極）と、絶縁性誘電体層１４の層と、
その上又はその頂部に置かれた２つの金属接点２０及び
２２（ソース及びドレイン電極）とを含む薄膜トランジ
スタ構造体１０の概略図である。金属接点２０及び２２
の上と間にはポリチオフェン半導体層１２がある。FIG. 1 shows a substrate 16, a metal contact 18 (gate electrode) in contact therewith, a layer of an insulating dielectric layer 14,
1 is a schematic diagram of a thin film transistor structure 10 including two metal contacts 20 and 22 (source and drain electrodes) placed on or on top of it. Metal contacts 20 and 22
There is a polythiophene semiconductor layer 12 between and above.
【００３０】図２は、基板３６と、ゲート電極３８と、
ソース電極４０と、ドレイン電極４２と、絶縁性誘電体
層３４と、ポリチオフェン半導体層３２とを含む、別の
薄膜トランジスタ構造体３０の概略図である。FIG. 2 shows a substrate 36, a gate electrode 38,
FIG. 5 is a schematic diagram of another thin film transistor structure 30 including a source electrode 40, a drain electrode 42, an insulating dielectric layer 34, and a polythiophene semiconductor layer 32.
【００３１】図３は、ゲート電極として作用する高濃度
ｎ−ドープシリコンウエハ５６と、熱により生成した酸
化ケイ素誘電体層５４と、ポリチオフェン半導体層５２
と、その上に置かれたソース電極６０とドレイン電極６
２とを含む薄膜トランジスタ構造体５０の概略図であ
る。FIG. 3 shows a heavily n-doped silicon wafer 56 acting as a gate electrode, a thermally generated silicon oxide dielectric layer 54, and a polythiophene semiconductor layer 52.
And the source electrode 60 and the drain electrode 6 placed thereon.
2 is a schematic diagram of a thin film transistor structure 50 including 2 and FIG.
【００３２】図４は、基板７６と、ゲート電極７８と、
ソース電極８０と、ドレイン電極８２と、ポリチオフェ
ン半導体層７２と、絶縁性誘電体層７４とを含む、別の
薄膜トランジスタ構造体７０の概略図である。FIG. 4 shows a substrate 76, a gate electrode 78,
FIG. 6 is a schematic diagram of another thin film transistor structure 70 including a source electrode 80, a drain electrode 82, a polythiophene semiconductor layer 72, and an insulating dielectric layer 74.
【００３３】本発明の一部の実施の形態では、必要に応
じて、図１〜図４の各トランジスタ構造体の上に保護層
を加えても良い。図４の薄膜トランジスタ構造体では、
絶縁性誘電体層７４は保護層として機能することもでき
る。In some embodiments of the invention, a protective layer may be added over each transistor structure of FIGS. 1-4, if desired. In the thin film transistor structure of FIG.
The insulating dielectric layer 74 can also function as a protective layer.
【００３４】基板層は一般に、目的とする用途に応じ
て、様々な適当な形のシリコンを含むシリコン材料、ガ
ラス板、プラスチックフィルム又はシート、等である。
構造可撓性のデバイスでは、例えば、ポリエステル、ポ
リカーボネート、ポリイミドシート等のプラスチック基
板が望ましい。基板の厚さは、約１０μｍ〜１０ｍｍ以
上であり、詳細な厚さは、特に可撓性のプラスチック基
板では約５０〜約１００μｍ、ガラス又はシリコンなど
の堅牢な基板では約１〜約１０ｍｍである。The substrate layer is generally a silicon material, including various suitable forms of silicon, glass plate, plastic film or sheet, etc., depending on the intended use.
For structurally flexible devices, plastic substrates such as polyester, polycarbonate, polyimide sheets are desirable. The thickness of the substrate is about 10 μm to 10 mm or more, and the detailed thickness is about 50 to about 100 μm, especially for a flexible plastic substrate, and about 1 to about 10 mm for a robust substrate such as glass or silicon. .
【００３５】ゲート電極をソース及びドレイン電極と隔
て、半導体層に接している絶縁性誘電体層は一般に、無
機材料膜、有機ポリマー膜、又は有機−無機複合材膜と
することができる。誘電体層の厚さは、例えば約１０ｎ
ｍ〜約１μｍ、より詳細な厚さは約１００〜約５００ｎ
ｍである。誘電体層に適した無機材料の具体例として
は、酸化ケイ素、窒化ケイ素、酸化アルミニウム、チタ
ン酸バリウム、ジルコン酸チタン酸バリウム、等が挙げ
られ、誘電体層に適した有機ポリマーの具体例として
は、ポリエステル類、ポリカーボネート類、ポリ（ビニ
ルフェノール）、ポリイミド類、ポリスチレン、ポリ
（メタクリレート）類、ポリ（アクリレート）類、エポ
キシ樹脂、等が挙げられ、無機−有機複合材料の具体例
としては、ポリエステル、ポリイミド、エポキシ樹脂等
のポリマー中に分散した超微小金属酸化物粒子などが挙
げられる。絶縁性誘電体層の厚さは通常、使用する誘電
体材料の比誘電率に応じて約５０〜約５００ｎｍであ
る。より詳細には、誘電体材料は約３以上の比誘電率を
持つため、約３００ｎｍの適当な誘電体の厚さがあれば
望ましい静電容量、例えば約１０-9〜約１０-7Ｆ／ｃｍ
2とすることができる。The insulating dielectric layer separating the gate electrode from the source and drain electrodes and in contact with the semiconductor layer can generally be an inorganic material film, an organic polymer film, or an organic-inorganic composite material film. The thickness of the dielectric layer is, for example, about 10n.
m to about 1 μm, more detailed thickness is about 100 to about 500 n
m. Specific examples of the inorganic material suitable for the dielectric layer include silicon oxide, silicon nitride, aluminum oxide, barium titanate, barium zirconate titanate, and the like, and specific examples of the organic polymer suitable for the dielectric layer. Are polyesters, polycarbonates, poly (vinylphenol), polyimides, polystyrene, poly (methacrylate) s, poly (acrylate) s, epoxy resins, and the like. Specific examples of the inorganic-organic composite material include: Examples include ultrafine metal oxide particles dispersed in a polymer such as polyester, polyimide and epoxy resin. The thickness of the insulating dielectric layer is typically about 50 to about 500 nm, depending on the dielectric constant of the dielectric material used. More specifically, since the dielectric material has a relative dielectric constant of about 3 or greater, a suitable dielectric thickness of about 300 nm provides a desired capacitance, eg, about 10 -9 to about 10 -7 F /. cm
It can be 2 .
【００３６】誘電体層とソース／ドレイン電極との間に
接して、本願に述べるポリチオフェン類を含む活性半導
体層を置く。この層の厚さは通常約１０ｎｍ〜約１μ
ｍ、又は約４０〜約１００ｎｍである。この層は通常、
スピンコーティング、キャスティング、スクリーン、ス
タンプ、又はジェット印刷などの溶液処理によって本発
明のポリチオフェン類の溶液から製造可能である。An active semiconductor layer containing the polythiophenes described in the present application is placed in contact with the dielectric layer and the source / drain electrodes. The thickness of this layer is usually about 10 nm to about 1 μm.
m, or about 40 to about 100 nm. This layer is usually
It can be produced from the solution of the polythiophenes of the present invention by solution treatment such as spin coating, casting, screen, stamping or jet printing.
【００３７】ゲート電極は、金属薄膜、導電性ポリマー
膜、導電性インキ又はペーストから作った導電性膜、あ
るいは基板自体（例えば、高濃度にドープしたシリコ
ン）とすることができる。ゲート電極材料の例として
は、アルミニウム、金、クロム、酸化インジウムスズ、
導電性ポリマー類、導電性インキ／ペースト等が挙げら
れるが、これらに限るものではない。導電性ポリマー
は、ポリスチレンスルホナートをドープしたポリ（３，
４−エチレンジオキシチオフェン）（ＰＳＳ−／ＰＥＤ
ＯＴ）などであり、導電性インキ／ペーストは、カーボ
ンブラック／グラファイト又はコロイド状の銀をポリマ
ーバインダ中に分散したもの（例えば、アチソン・コロ
イズ社（Acheson Colloids Company）製のエレクトロダ
グ（ELECTRODAG））や、銀を充填した導電性熱可塑性イ
ンキ（ノエル・インダストリーズ（Noelle Industrie
s）製）である。ゲート層は、真空蒸着、金属や導電性
金属酸化物のスパッタリング、導電性ポリマー溶液又は
導電性インキのスピンコーティング、キャスティング、
又は印刷による塗布によって調製できる。ゲート電極層
の厚さは約１０ｎｍ〜約１０μｍの範囲であり、金属薄
膜に望ましい厚さは約１０〜約２００ｎｍの範囲であ
り、ポリマー導電体では約１〜約１０μｍの範囲であ
る。The gate electrode can be a thin metal film, a conductive polymer film, a conductive film made from a conductive ink or paste, or the substrate itself (eg heavily doped silicon). Examples of gate electrode materials include aluminum, gold, chromium, indium tin oxide,
Examples include conductive polymers and conductive inks / pastes, but are not limited to these. The conductive polymer is poly (3,3) doped with polystyrene sulfonate.
4-ethylenedioxythiophene) (PSS- / PED
The conductive ink / paste is carbon black / graphite or colloidal silver dispersed in a polymer binder (for example, ELECTRODAG manufactured by Acheson Colloids Company). Or conductive thermoplastic ink filled with silver (Noelle Industrie
s)). The gate layer is formed by vacuum deposition, sputtering of metal or conductive metal oxide, spin coating of conductive polymer solution or conductive ink, casting,
Alternatively, it can be prepared by application by printing. The thickness of the gate electrode layer is in the range of about 10 nm to about 10 μm, the desired thickness for the metal thin film is in the range of about 10 to about 200 nm, and for the polymer conductor it is in the range of about 1 to about 10 μm.
【００３８】ソース及びドレイン電極層は、半導体層に
対して低抵抗オーム接触となる材料から製造することが
できる。ソース及びドレイン電極としての使用に適した
典型的な材料は、金、ニッケル、アルミニウム、プラチ
ナ、導電性ポリマー、導電性インキなどのゲート電極材
料として挙げられたものなどである。この層の典型的な
厚さは、例えば約４０ｎｍ〜約１μｍであり、より詳細
な厚さは約１００〜約４００ｎｍである。ＴＦＴデバイ
ス構造体は、幅Ｗ、長さＬの半導体チャネルから成る。
半導体チャネル幅は約１０μｍ〜約５ｍｍであり、望ま
しいチャネル幅は約１００μｍ〜約１ｍｍである。半導
体チャネル長さは約１μｍ〜約１ｍｍであり、より詳細
なチャネル長さは約５〜約１００μｍである。The source and drain electrode layers can be made from materials that make a low resistance ohmic contact to the semiconductor layer. Typical materials suitable for use as the source and drain electrodes include those listed as gate electrode materials such as gold, nickel, aluminum, platinum, conductive polymers, conductive inks, and the like. A typical thickness of this layer is, for example, about 40 nm to about 1 μm, and a more detailed thickness is about 100 to about 400 nm. The TFT device structure consists of semiconductor channels of width W and length L.
The semiconductor channel width is about 10 μm to about 5 mm, and the desired channel width is about 100 μm to about 1 mm. The semiconductor channel length is from about 1 μm to about 1 mm, and more detailed channel length is from about 5 to about 100 μm.
【００３９】ソース電極は接地しており、通常約＋１０
〜約−８０ボルトの電圧をゲート電極に印加したとき
に、半導体チャネルを通って移動する電荷キャリヤを集
めるため、通常約０〜約−８０ボルトのバイアス電圧を
ドレイン電極に印加する。The source electrode is grounded, usually about +10.
A bias voltage of about 0 to about -80 volts is typically applied to the drain electrode to collect charge carriers migrating through the semiconductor channel when a voltage of about -80 volts is applied to the gate electrode.
【００４０】[0040]
【実施例】ａ）デバイスの製造：基本的な供試デバイス
配置として、図１及び図３にそれぞれ図示したボトムコ
ンタクト型及びトップコンタクト型薄膜トランジスタ構
造体を用いた。ボトムコンタクト型供試デバイスは、ガ
ラス基板上に写真平板で予めパターンを形成した一連の
トランジスタの誘電体層と、規定のチャネル幅と長さの
電極とを含むものである。ガラス基板上のゲート電極は
厚さ約８０ｎｍのクロムから成るものであった。ゲート
誘電体は、約２２ｎＦ／ｃｍ2（ナノファラッド／平方
センチメートル）の静電容量を持つ、厚さ３００ｎｍの
窒化ケイ素であった。ゲート誘電体層の頂部又はその上
に被覆して、厚さ約１００ｎｍの金から成るソース及び
ドレイン接点を真空蒸着した。次に、厚さ約３０〜約１
００ｎｍの供試ポリチオフェン半導体層を、周囲の酸
素、湿気、又は光への暴露を防止する対策を何ら講じる
ことなく、周囲条件下でスピンコーティングにより塗布
した。半導体層の製造に用いた溶液は、適当な溶媒に溶
解した１重量％のポリチオフェンから成るものであり、
使用前に０．４５μｍのフィルタで濾過した。スピンコ
ーティングは、回転速度１，０００ｒｐｍで約３５秒間
行った。得られた被覆デバイスは、真空中８０℃で２０
時間乾燥した後、評価に供した。EXAMPLES a) Device manufacture: As a basic device arrangement for test, the bottom contact type and top contact type thin film transistor structures shown in FIGS. 1 and 3 were used. The bottom contact type device under test includes a series of transistor dielectric layers pre-patterned with a photolithographic plate on a glass substrate, and electrodes having prescribed channel widths and lengths. The gate electrode on the glass substrate was made of chromium having a thickness of about 80 nm. The gate dielectric was 300 nm thick silicon nitride with a capacitance of about 22 nF / cm 2 (nanofarads per square centimeter). Source and drain contacts of about 100 nm thick gold were vacuum deposited over or on top of the gate dielectric layer. Next, the thickness is about 30 to about 1
The 00 nm test polythiophene semiconductor layer was applied by spin coating under ambient conditions without any measures taken to prevent exposure to ambient oxygen, moisture, or light. The solution used for the production of the semiconductor layer consists of 1% by weight of polythiophene dissolved in a suitable solvent,
It was filtered with a 0.45 μm filter before use. Spin coating was performed at a rotation speed of 1,000 rpm for about 35 seconds. The obtained coated device is 20 at 80 ° C. in vacuum.
After drying for an hour, it was subjected to evaluation.
【００４１】トップコンタクト型供試デバイスは、ｎ−
ドープシリコンウエハと、その上に熱生成させた厚さ約
１１０ｎｍの酸化ケイ素層とを含む。ウエハがゲート電
極として機能する一方、酸化ケイ素層はゲート誘電体と
して働き、その静電容量は約３２ｎＦ／ｃｍ2であっ
た。シリコンウエハをまずメタノールで清浄にし、空気
乾燥後、０．０１Ｍの１，１，１，３，３，３−ヘキサ
メチルジシラザンのジクロロメタン溶液に、室温（２２
〜２５℃）で３０分間浸した。次にこのウエハをジクロ
ロメタンで洗い、乾燥した。スピンコーティングによ
り、厚さ約３０〜約１００ｎｍの半導体ポリチオフェン
層を酸化ケイ素誘電体層の上に塗布し、真空中８０℃で
２０時間乾燥した。デバイス製造の際、周囲の酸素、湿
気、又は光への材料の暴露を防止する対策は講じなかっ
た。次に、金のソース及びドレイン電極を、半導体ポリ
チオフェン層の上に、様々なチャネル長さと幅のシャド
ウマスクを通して真空蒸着し、様々な大きさの一連のト
ランジスタを製作した。念のため製造後のデバイスは、
評価の前後には相対湿度約３０％の乾燥雰囲気中、暗所
で保存した。The top contact type device under test is n-
It includes a doped silicon wafer with a thermally generated silicon oxide layer about 110 nm thick. The silicon oxide layer acted as the gate dielectric, while the wafer acted as the gate electrode, and its capacitance was about 32 nF / cm 2 . The silicon wafer was first cleaned with methanol, air-dried and then placed in a 0.01 M solution of 1,1,1,3,3,3-hexamethyldisilazane in dichloromethane at room temperature (22
Soak for 30 minutes at -25 ° C. The wafer was then washed with dichloromethane and dried. A semiconductor polythiophene layer with a thickness of about 30 to about 100 nm was applied onto the silicon oxide dielectric layer by spin coating and dried in vacuum at 80 ° C. for 20 hours. No measures were taken during device manufacture to prevent exposure of the material to ambient oxygen, moisture, or light. Next, gold source and drain electrodes were vacuum deposited on the semiconductor polythiophene layer through a shadow mask of various channel lengths and widths to fabricate a series of transistors of various sizes. Just in case, the device after manufacturing is
Before and after the evaluation, it was stored in a dark place in a dry atmosphere with a relative humidity of about 30%.
【００４２】ｂ）ＴＦＴデバイスの特性評価：電界効果
トランジスタの性能を、キースリー（Keithley）４２０
０ＳＣＳ半導体特性評価デバイスを用いて、暗箱中周囲
条件で評価した。キャリヤ移動度（μ）は、飽和領域
（ゲート電圧、ＶG＜ソース−ドレイン電圧、ＶSD）に
おけるデータより、下記の式（１）に従って計算した。B) TFT device characterization: Keithley 420 performance of field effect transistors
Using a 0SCS semiconductor property evaluation device, evaluation was performed in a dark box under ambient conditions. The carrier mobility (μ) was calculated according to the following formula (1) from the data in the saturation region (gate voltage, V G <source-drain voltage, V SD ).
【００４３】[0043]
【式１】
ＩSD＝Ｃiμ（Ｗ／２Ｌ）（ＶG−ＶT）2 （１）
式中、ＩSDは飽和領域におけるドレイン電流であり、Ｗ
とＬはそれぞれ半導体チャネルの幅と長さであり、Ｃi
はゲート誘電体層の単位面積当たりの静電容量であり、
ＶG及びＶTはそれぞれ、ゲート電圧及びしきい電圧であ
る。このデバイスのＶTは、飽和領域におけるＩSDの平
方根と、測定データからＩSD＝０を外挿して求めたデバ
イスのＶGとの関係から求めた。In [Equation 1] I SD = C i μ (W / 2L) (V G -V T) 2 (1) formula, I SD is the drain current at the saturated regime, W
And L are the width and length of the semiconductor channel, respectively, and C i
Is the capacitance per unit area of the gate dielectric layer,
V G and V T are the gate voltage and the threshold voltage, respectively. The V T of this device was obtained from the relationship between the square root of I SD in the saturation region and V G of the device obtained by extrapolating I SD = 0 from the measurement data.
【００４４】薄膜トランジスタの特性を表す値は、その
電流オン／オフ比である。これはゲート電圧ＶGがドレ
イン電圧ＶDと等しいかそれ以上であるときの飽和ソー
ス−ドレイン電流と、ゲート電圧ＶGがゼロの時のソー
ス−ドレイン電流との比である。A value representing the characteristic of the thin film transistor is its current on / off ratio. This is the ratio of the saturated source-drain current when the gate voltage V G is equal to or higher than the drain voltage V D and the source-drain current when the gate voltage V G is zero.
【００４５】比較例
公知の位置規則性ポリチオフェン、ポリ（３−ヘキシル
チオフェン−２，５−ジイル）を用いる以外は本質的に
前記の手順を繰り返して、図１及び図３にそれぞれ示し
たボトムコンタクト型デバイス及びトップコンタクト型
デバイスを製作した。この材料はアルドリッチ・ケミカ
ル（Aldrich Chemical）より購入し、そのクロロベンゼ
ン溶液からメタノールへの沈殿を３回繰り返して精製し
た。 Comparative Example Essentially the above procedure was repeated except that the known regioregular polythiophene, poly (3-hexylthiophene-2,5-diyl), was used to obtain the bottom contacts shown in FIGS. 1 and 3, respectively. Type device and top contact type device were manufactured. This material was purchased from Aldrich Chemical and purified by repeating its precipitation from chlorobenzene solution into methanol three times.
【００４６】半導体ポリチオフェン層は、前述の手法に
従い、１重量％の位置規則性ポリ（３−ヘキシルチオフ
ェン−２，５−ジイル）のクロロベンゼン溶液のスピン
コーティングにより、周囲条件下でデバイス上に被覆し
た。このデバイスは、評価前に真空中８０℃で２０時間
乾燥した。各デバイスに対し５個以上のトランジスタか
ら得た平均特性値を次にまとめた。
（１） ボトムコンタクト型デバイス（Ｗ＝１，０００
μｍ，Ｌ＝１０μｍ）
移動度：１〜２．３×１０-3ｃｍ2／Ｖ．ｓｅｃ
初期電流オン／オフ比：０．８〜１×１０3
５日後の電流オン／オフ比：５〜１０
（２） トップコンタクト型デバイス（Ｗ＝５，０００
μｍ，Ｌ＝６０μｍ）
移動度：１〜１．２×１０-2ｃｍ2／Ｖ．ｓｅｃ
初期電流オン／オフ比：１．５〜２．１×１０3
５日後の電流オン／オフ比：５〜１０The semiconducting polythiophene layer was coated on the device under ambient conditions by spin coating of a 1% by weight solution of regioregular poly (3-hexylthiophene-2,5-diyl) in chlorobenzene according to the procedure described above. . This device was dried in vacuum at 80 ° C. for 20 hours before evaluation. The average characteristic values obtained from 5 or more transistors for each device are summarized below. (1) Bottom contact device (W = 1,000
μm, L = 10 μm) Mobility: 1 to 2.3 × 10 −3 cm 2 / V. sec initial current on / off ratio: 0.8 to 1 × 10 3 5 days after current on / off ratio of: 5 to 10 (2) Top-contact device (W = 5,000
μm, L = 60 μm) Mobility: 1 to 1.2 × 10 −2 cm 2 / V. sec initial current on / off ratio: 1.5 to 2.1 × 10 3 5 days after current on / off ratio of: 5 to 10
【００４７】観察された初期電流オン／オフ比が低いの
は、ポリ（３−ヘキシルチオフェン−２，５−ジイル）
が酸化的ドーピングを受け易く、すなわち環境酸素の存
在下ではポリ（３−ヘキシルチオフェン−２，５−ジイ
ル）が不安定であることを示している。僅か５日間のう
ちに電流オン／オフ比が著しく減少するのも、周囲条件
でのポリ（３−ヘキシルチオフェン−２，５−ジイル）
の甚だしい機能不安定性を更に裏付けている。The low initial current on / off ratio observed is due to poly (3-hexylthiophene-2,5-diyl).
Are susceptible to oxidative doping, ie, poly (3-hexylthiophene-2,5-diyl) is unstable in the presence of ambient oxygen. The current on / off ratio is significantly reduced in only 5 days because the poly (3-hexylthiophene-2,5-diyl) at ambient conditions
It further supports the immense functional instability of.
【００４８】実施例
（ａ）ポリ［２，５−ビス（２−チエニル）−３，４−
ジオクチルチオフェン］（２）の合成
ｉ）モノマーの合成：ポリチオフェン（２）の調製に用
いるモノマー、２，５−ビス（５−ブロモ−２−チエニ
ル）−３，４−ジオクチルチオフェンを次のように合成
した。 Example (a) Poly [2,5-bis (2-thienyl) -3,4-
Synthesis of Dioctylthiophene] (2) i) Synthesis of Monomer: Monomer used to prepare polythiophene (2), 2,5-bis (5-bromo-2-thienyl) -3,4-dioctylthiophene, was prepared as follows. Synthesized.
【００４９】３，４−ジオクチルチオフェン：不活性雰
囲気中、氷浴で冷却した５００ｍｌの丸底フラスコ中
で、２００ｍｌの無水ジエチルエーテルに溶解したジク
ロロ［１，３−ビス（ジフェニルホスフィノ）プロパ
ン］ニッケル（II）（０．２ｇ）と、３，４−ジブロモ
チオフェン（２０．１６ｇ、０．０８３３ｍｏｌ）との
混合物を良くかき混ぜながら、これに２Ｍのオクチルマ
グネシウム＝ブロミド（１００ｍｌ、０．２ｍｏｌ）の
無水ジエチルエーテル溶液を加えた。ニッケル錯体はす
ぐにグリニャール試薬と反応し、得られた反応混合物を
室温まで暖まるに任せた。発熱反応は３０分以内に始ま
り、ジエチルエーテルが穏やかに還流し始めた。更に２
時間室温で撹拌後、反応混合物を６時間還流し、氷浴で
冷やし、２Ｎの塩酸水溶液で加水分解した。有機層を分
け、水で、次に塩水で洗い、再び水で洗った後、無水硫
酸ナトリウムに通して乾燥させた。溶媒を蒸発後、残留
物をクーゲルロア（Kugelrohr）デバイスに通して減圧
下で蒸留し、無色液体として２１．３ｇの３，４−ジオ
クチルチオフェンを得た。1
Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ６．８９（ｓ，２Ｈ），
２．５０（ｔ，Ｊ＝７．０Ｈｚ，４Ｈ），１．６４−
１．５８（ｍ，４Ｈ）， １．
４０−１．２８（ｍ，２０Ｈ），０．８９（ｔ，
Ｊ＝６．５Ｈｚ，６Ｈ）13
Ｃ−ＮＭＲ（ＣＤＣｌ3）：δ１４２．１，１１９．
８，３１．９，２９．６（２Ｃ），２９．５，２９．
３，２８．８，２２．７，１４．１3,4-Dioctylthiophene: Dichloro [1,3-bis (diphenylphosphino) propane] dissolved in 200 ml of anhydrous diethyl ether in a 500 ml round bottom flask cooled in an ice bath in an inert atmosphere. A mixture of nickel (II) (0.2 g) and 3,4-dibromothiophene (20.16 g, 0.0833 mol) was stirred well while adding 2M octylmagnesium bromide (100 ml, 0.2 mol). Anhydrous diethyl ether solution was added. The nickel complex immediately reacted with the Grignard reagent and the resulting reaction mixture was allowed to warm to room temperature. The exothermic reaction started within 30 minutes and the diethyl ether began to reflux gently. 2 more
After stirring for an hour at room temperature, the reaction mixture was refluxed for 6 hours, cooled in an ice bath and hydrolyzed with 2N aqueous hydrochloric acid. The organic layer was separated, washed with water, then with brine, again with water, and then dried over anhydrous sodium sulfate. After evaporation of the solvent, the residue was distilled under reduced pressure through a Kugelrohr device to give 21.3 g of 3,4-dioctylthiophene as a colorless liquid. 1 H-NMR (CDCl 3 ): δ 6.89 (s, 2H),
2.50 (t, J = 7.0 Hz, 4H), 1.64-
1.58 (m, 4H), 1.
40-1.28 (m, 20H), 0.89 (t,
J = 6.5 Hz, 6 H) 13 C-NMR (CDCl 3 ): δ142.1, 119.
8, 31.9, 29.6 (2C), 29.5, 29.
3,28.8, 22.7, 14.1
【００５０】２，５−ジブロモ−３，４−ジオクチルチ
オフェン：１００ｍｌの丸底フラスコ中で、３０ｍｌの
ジクロロメタンと１０ｍｌの酢酸との混合物に溶解した
３，４−ジオクチルチオフェン（３．６ｇ、１１．７ｍ
ｍｏｌ）の溶液を良く撹拌しながら、これにＮ−ブロモ
スクシンイミド（４．６ｇ、２５．７ｍｍｏｌ）を加え
た。薄層クロマトグラフ法により反応の様子を観察した
ところ、約３５分で完了した。この混合物を１６０ｍｌ
のジクロロメタンで希釈し、濾過してスクシンイミドを
除いた。濾液を２Ｎの水酸化ナトリウム水溶液で洗い、
次に水で２回洗った（２×１００ｍｌ）。無水硫酸ナト
リウムで乾燥後溶媒を除き、淡黄色の液体として５．４
ｇの２，５−ジブロモ−３，４−ジオクチルチオフェン
を得た。1
Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ２．５０（ｔ，Ｊ＝７．
０Ｈｚ，４Ｈ），１．５２−１．２８（ｍ，２４Ｈ），
０．８９（ｔ，Ｊ＝６．５Ｈｚ，６Ｈ）2,5-Dibromo-3,4-dioctylthiophene: In a 100 ml round bottom flask, 3,4-dioctylthiophene (3.6 g, 11.g) dissolved in a mixture of 30 ml dichloromethane and 10 ml acetic acid. 7 m
N-bromosuccinimide (4.6 g, 25.7 mmol) was added to this while thoroughly stirring the solution of (mol). When the reaction state was observed by thin layer chromatography, it was completed in about 35 minutes. 160 ml of this mixture
Of dichloromethane and filtered to remove succinimide. Wash the filtrate with 2N aqueous sodium hydroxide,
It was then washed twice with water (2 x 100 ml). After drying over anhydrous sodium sulfate, the solvent was removed to obtain 5.4 as a pale yellow liquid.
g of 2,5-dibromo-3,4-dioctylthiophene was obtained. 1 H-NMR (CDCl 3 ): δ2.50 (t, J = 7.
0Hz, 4H), 1.52-1.28 (m, 24H),
0.89 (t, J = 6.5Hz, 6H)
【００５１】２，５−ビス（２−チエニル）−３，４−
ジオクチルチオフェン：不活性雰囲気中の乾燥箱の中、
２５０ｍｌの丸底フラスコ中で、無水テトラヒドロフラ
ン（５０ｍｌ）に溶解した、２，５−ジブロモ−３，４
−ジオクチルチオフェン（４．２ｇ、９．０ｍｍｏｌ）
と、２−（トリブチルスズ）チオフェン（７．４ｇ、１
９．８ｍｍｏｌ）との混合物に、Ｐｄ（ＰＰｈ3）2Ｃｌ
2（０．１５ｇ，０．２ｍｍｏｌ）を加えた。次にこの
混合物を１２時間還流し、溶媒を留去した。こうして得
られた粗生成物を、溶離液としてヘキサンを用いたシリ
カゲル上でのフラッシュ（flash）クロマトグラフ法に
より精製し、３．１ｇの２，５−ビス（２−チエニル）
−３，４−ジオクチルチオフェンを得た。1
Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ７．３１（ｄｄ，Ｊ＝
３．２，０．５Ｈｚ，２Ｈ），７．１３（ｄｄ，Ｊ＝
２．２，０．５Ｈｚ，２Ｈ），７．０６（ｄｄ，Ｊ＝
２．２，４．５Ｈｚ， ２
Ｈ），２．６８（ｄｄ，Ｊ＝７．６，７．６Ｈｚ，
４Ｈ），１．５９−１．５３
（ｍ，４Ｈ），１．４２−１．２７（ｍ，２０Ｈ），
０．９１（ｔ，Ｊ＝６．５Ｈｚ，６Ｈ）2,5-bis (2-thienyl) -3,4-
Dioctylthiophene: In a dry box in an inert atmosphere,
2,5-dibromo-3,4 dissolved in anhydrous tetrahydrofuran (50 ml) in a 250 ml round bottom flask.
-Dioctylthiophene (4.2 g, 9.0 mmol)
And 2- (tributyltin) thiophene (7.4 g, 1
9.8 mmol) and Pd (PPh 3 ) 2 Cl
2 (0.15 g, 0.2 mmol) was added. The mixture was then refluxed for 12 hours and the solvent was evaporated. The crude product thus obtained was purified by flash chromatography on silica gel using hexane as the eluent to give 3.1 g of 2,5-bis (2-thienyl).
-3,4-Dioctylthiophene was obtained. 1 H-NMR (CDCl 3 ): δ7.31 (dd, J =
3.2, 0.5 Hz, 2H), 7.13 (dd, J =
2.2, 0.5Hz, 2H), 7.06 (dd, J =
2.2, 4.5Hz, 2
H), 2.68 (dd, J = 7.6, 7.6 Hz,
4H), 1.59-1.53
(M, 4H), 1.42-1.27 (m, 20H),
0.91 (t, J = 6.5Hz, 6H)
【００５２】２，５−ビス（５−ブロモ−２−チエニ
ル）−３，４−ジオクチルチオフェン：氷浴で冷却した
１００ｍｌの丸底フラスコ中で、Ｎ，Ｎ−ジメチルホル
ムアミド（３０ｍｌ）に溶解した２，５−ビス（２−チ
エニル）−３，４−ジオクチルチオフェン（３．６ｇ、
７．６ｍｍｏｌ）の溶液を良く撹拌しながら、これにＮ
−ブロモスクシンイミド（２．８ｇ、１５．７ｍｍｏ
ｌ）を加えた。添加後、混合物がゆっくりと室温まで暖
まるに任せた。薄層クロマトグラフ法で反応を観察した
ところ、３時間後には反応は止まった。得られた混合物
をヘキサン（１７０ｍｌ）で希釈し、１００ｍｌの水で
３回洗った。有機層を分け、無水硫酸ナトリウムで乾燥
し、真空蒸発させて粗生成物を得た。これを、溶離液と
してヘキサンを用いたシリカゲル上のフラッシュクロマ
トグラフ法により精製し、２．５ｇの２，５−ビス（５
−ブロモ−２−チエニル）−３，４−ジオクチルチオフ
ェンを得た。1
Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ７．０６（ｄ，Ｊ＝３．
５Ｈｚ，２Ｈ），６．８６（ｄ，Ｊ＝３．５Ｈｚ，２
Ｈ），２．６２（ｄｄ， Ｊ＝
７．３，７．３Ｈｚ，４Ｈ），１．５５−１．４９
（ｍ，４Ｈ），１．４１−１．２８（ｍ，２０Ｈ），
０．８９（ｔ，Ｊ＝６．５Ｈｚ，６Ｈ）13
Ｃ−ＮＭＲ（ＣＤＣｌ3）；δ１４０．６，１３７．
４，１３０．２，１２９．
３，１２６．２，１１２．０，３１．９，３０．８，
２９．８，２９．２（２Ｃ），
２８．１，２２．７， １４．
２2,5-Bis (5-bromo-2-thienyl) -3,4-dioctylthiophene: dissolved in N, N-dimethylformamide (30 ml) in a 100 ml round bottom flask cooled in an ice bath. 2,5-bis (2-thienyl) -3,4-dioctylthiophene (3.6 g,
7.6 mmol) solution with good stirring and
-Bromosuccinimide (2.8 g, 15.7 mmo
l) was added. After the addition, the mixture was allowed to slowly warm to room temperature. When the reaction was observed by thin layer chromatography, the reaction stopped after 3 hours. The resulting mixture was diluted with hexane (170 ml) and washed 3 times with 100 ml water. The organic layer was separated, dried over anhydrous sodium sulfate and evaporated in vacuo to give a crude product. This was purified by flash chromatography on silica gel using hexane as the eluent, 2.5 g of 2,5-bis (5
-Bromo-2-thienyl) -3,4-dioctylthiophene was obtained. 1 H-NMR (CDCl 3 ): δ 7.06 (d, J = 3.
5Hz, 2H), 6.86 (d, J = 3.5Hz, 2
H), 2.62 (dd, J =
7.3, 7.3 Hz, 4H), 1.55-1.49
(M, 4H), 1.41-1.28 (m, 20H),
0.89 (t, J = 6.5 Hz, 6H) 13 C-NMR (CDCl 3 ); δ 140.6, 137.
4, 130.2, 129.
3,126.2, 112.0, 31.9, 30.8,
29.8, 29.2 (2C),
28.1, 22.7, 14.
Two
【００５３】ポリ［２，５−ビス（２−チエニル）−
３，４−ジオクチルチオフェン］（２）：無水テトラヒ
ドロフラン（１０ｍｌ）に溶解した２，５−ビス（５−
ブロモ−２−チエニル）−３，４−ジオクチルチオフェ
ン（２．４６ｇ、３．９ｍｍｏｌ）の溶液に、調製直後
のレイケＺｎ（０．２８ｇ，４．２９ｍｍｏｌ）を無水
テトラヒドロフラン（２０ｍｌ）に懸濁したものを良く
撹拌しながら、不活性雰囲気中で滴下して加え、この混
合物を４５分間室温で反応させた。次に、無水テトラヒ
ドロフラン（３５ｍｌ）に懸濁させたＮｉ（ｄｐｐｅ）
Ｃｌ2（０．０２１ｇ、０．０４ｍｍｏｌ）を注意しな
がら加えた。反応混合物を６０℃で３時間加熱後、２Ｎ
の塩酸−メタノール溶液中に注いだ。沈殿したポリチオ
フェン生成物を濾過し、７０ｍｌの熱テトラヒドロフラ
ンに再溶解し、２Ｎのアンモニア−メタノール溶液から
沈殿させた。この操作を２度繰り返し、酸とオリゴマー
とを除いた。真空中、室温で乾燥後、１．６ｇの、Ｍw
４１，９００、Ｍn１１，８００Ｋ、Ｔｍ１８０℃のポ
リ［２，５−ビス（２−チエニル）−３，４−ジオクチ
ルチオフェン］（２）を得た。1
Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ７．３０，７．１３，
７．０５，２．７３，１．５９，１．４５，１．２９，
０．８９13
Ｃ−ＮＭＲ（ＣＤＣｌ3）：δ１４０．４，１３６．
７，１３５．１，１２９．
８，１２６．４，１２３．９，３１．９，３０．７，
２９．９，２９．３，２８．
３，２２．７，１４．２Poly [2,5-bis (2-thienyl)-
3,4-Dioctylthiophene] (2): 2,5-bis (5- dissolved in anhydrous tetrahydrofuran (10 ml)
In a solution of bromo-2-thienyl) -3,4-dioctylthiophene (2.46 g, 3.9 mmol), Reike Zn (0.28 g, 4.29 mmol) immediately after preparation was suspended in anhydrous tetrahydrofuran (20 ml). One was added dropwise with good stirring in an inert atmosphere and the mixture was allowed to react for 45 minutes at room temperature. Next, Ni (dppe) suspended in anhydrous tetrahydrofuran (35 ml)
Cl 2 (0.021 g, 0.04 mmol) was added carefully. After heating the reaction mixture at 60 ° C. for 3 hours, 2N
Of hydrochloric acid-methanol solution. The precipitated polythiophene product was filtered, redissolved in 70 ml hot tetrahydrofuran and precipitated from a 2N ammonia-methanol solution. This operation was repeated twice to remove the acid and the oligomer. After drying in vacuum at room temperature, 1.6 g of M w
41,900, to give M n 11,800K, Tm180 ℃ of poly [2,5-bis (2-thienyl) -3,4-dioctyl thiophene] (2). 1 H-NMR (CDCl 3 ): δ7.30, 7.13,
7.05, 2.73, 1.59, 1.45, 1.29,
0.89 13 C-NMR (CDCl 3 ): δ140.4,136.
7, 135.1, 129.
8, 126.4, 123.9, 31.9, 30.7,
29.9, 29.3, 28.
3, 22.7, 14.2
【００５４】図１及び図３にそれぞれ図示した、ひとつ
はボトムコンタクト型もうひとつはトップコンタクト型
配置の２つの供試デバイスを、前述の製造手順に従い上
記のポリチオフェンを用いて製造した。デバイスは、評
価の前に真空中８０℃で２０時間乾燥させた。各デバイ
スに対し５個以上のトランジスタから得た平均特性値を
次にまとめた。
（１）ボトムコンタクト型デバイス（Ｗ＝１，０００μ
ｍ、Ｌ＝１０μｍ）
移動度：３．４×１０-4〜１．３×１０-3ｃｍ2／Ｖ．
ｓｅｃ
初期電流オン／オフ比：０．８〜１．３×１０4
５日後の電流オン／オフ比：５．０〜７．０×１０3
（２）トップコンタクト型デバイス（Ｗ＝５，０００μ
ｍ、Ｌ＝６０μｍ）
移動度：１．３〜３．１×１０-3ｃｍ2／Ｖ．ｓｅｃ
初期電流オン／オフ比：１．５〜２．６×１０5
５日後の電流オン／オフ比：１．１〜２．０×１０5
３０日後の電流オン／オフ比：８．０〜９．５×１０4 Two test devices, one of which is a bottom contact type and the other of which is a top contact type, shown in FIGS. 1 and 3, respectively, were manufactured using the above polythiophene according to the manufacturing procedure described above. The device was dried at 80 ° C. in vacuum for 20 hours before evaluation. The average characteristic values obtained from 5 or more transistors for each device are summarized below. (1) Bottom contact device (W = 1,000μ
m, L = 10 μm) Mobility: 3.4 × 10 −4 to 1.3 × 10 −3 cm 2 / V.
sec Initial current on / off ratio: 0.8 to 1.3 × 10 4 Current on / off ratio after 5 days: 5.0 to 7.0 × 10 3 (2) Top contact type device (W = 5,000 μ)
m, L = 60 μm) Mobility: 1.3 to 3.1 × 10 −3 cm 2 / V. sec Initial current on / off ratio: 1.5 to 2.6 × 10 5 Current on / off ratio after 5 days: 1.1 to 2.0 × 10 5 Current on / off ratio after 30 days: 8.0 9.5 x 10 4
【００５５】初期電流オン／オフ比が大きく、時間を経
ても電流オン／オフ比の低下が遅いことから、本発明の
実施の形態のポリチオフェン半導体層が安定であること
が示された。Since the initial current on / off ratio is large and the current on / off ratio decreases slowly over time, it is shown that the polythiophene semiconductor layer of the embodiment of the present invention is stable.
【図１】 本発明によるポリチオフェン類の実施の形態
を用いた薄膜トランジスタ構造体の概略図である。FIG. 1 is a schematic view of a thin film transistor structure using an embodiment of polythiophenes according to the present invention.
【図２】 本発明によるポリチオフェン類の実施の形態
を用いた別の薄膜トランジスタ構造体の概略図である。FIG. 2 is a schematic diagram of another thin film transistor structure using an embodiment of polythiophenes according to the present invention.
【図３】 本発明によるポリチオフェン類の実施の形態
を用いた別の薄膜トランジスタ構造体の概略図である。FIG. 3 is a schematic diagram of another thin film transistor structure using an embodiment of polythiophenes according to the present invention.
【図４】 本発明によるポリチオフェン類の実施の形態
を用いた別の薄膜トランジスタ構造体の概略図である。FIG. 4 is a schematic diagram of another thin film transistor structure using an embodiment of polythiophenes according to the present invention.
１ 薄膜トランジスタ構造体、１２ ポリチオフェン半
導体層、１４ 絶縁性誘電体層、１６ 基板、１８ ゲ
ート電極、２０ ソース電極、２２ ドレイン電極、３
０ 薄膜トランジスタ構造体、３２ ポリチオフェン半
導体層、３４絶縁性誘電体層、３６ 基板、３８ ゲー
ト電極、４０ ソース電極、４２ ドレイン電極、５０
薄膜トランジスタ構造体、５２ ポリチオフェン半導
体層、５４ 酸化ケイ素誘電体層、５６ シリコンウエ
ハ、６０ ソース電極、６２ドレイン電極、７０ 薄膜
トランジスタ構造体、７２ ポリチオフェン半導体層、
７４ 絶縁性誘電体層、７６ 基板、７８ ゲート電
極、８０ ソース電極、８２ ドレイン電極。1 thin film transistor structure, 12 polythiophene semiconductor layer, 14 insulating dielectric layer, 16 substrate, 18 gate electrode, 20 source electrode, 22 drain electrode, 3
0 thin film transistor structure, 32 polythiophene semiconductor layer, 34 insulating dielectric layer, 36 substrate, 38 gate electrode, 40 source electrode, 42 drain electrode, 50
Thin film transistor structure, 52 Polythiophene semiconductor layer, 54 Silicon oxide dielectric layer, 56 Silicon wafer, 60 Source electrode, 62 Drain electrode, 70 Thin film transistor structure, 72 Polythiophene semiconductor layer,
74 insulating dielectric layer, 76 substrate, 78 gate electrode, 80 source electrode, 82 drain electrode.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 イリアン ウー カナダ オンタリオ ミッシソーガ ボナ ー ロード 2360 アパートメント 1004 (72)発明者 ダサラオ ケイ ムルチ カナダ オンタリオ ミッシソーガ セイ ント ローレント コート 3667 Ｆターム(参考） 4J032 BA03 BA04 BA05 BA25 BB06 BC02 CA02 CA03 CA04 CA12 CA14 CB04 CB05 CD02 CD08 CE03 CG01 5F110 AA05 BB01 BB03 BB05 BB10 CC03 CC05 CC07 DD01 DD02 DD05 EE01 EE02 EE03 EE04 EE07 EE08 EE42 EE43 EE44 FF01 FF02 FF03 FF07 FF23 GG05 GG06 GG25 GG28 GG29 GG42 HK01 HK02 HK03 HK07 HK32 QQ06 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Irian Wu Canada Ontario Mississauga Bona ー Road 2360 Apartment 1004 (72) Inventor Dasarao Kei Murchi Canada Ontario Mississauga Say Troon Rent Court 3667 F-term (reference) 4J032 BA03 BA04 BA05 BA25 BB06 BC02 CA02 CA03 CA04 CA12 CA14 CB04 CB05 CD02 CD08 CE03 CG01 5F110 AA05 BB01 BB03 BB05 BB10 CC03 CC05 CC07 DD01 DD02 DD05 EE01 EE02 EE03 EE04 EE07 EE08 EE42 EE43 EE44 FF01 FF02 FF03 FF07 FF23 GG05 GG06 GG25 GG28 GG29 GG42 HK01 HK02 HK03 HK07 HK32 QQ06
Claims (9)
フェンを含む電子的デバイスであって、 【化１】 式中、Ｒ及びＲ’は側鎖であり、Ａは二価結合基であ
り、ｘ及びｙは非置換チエニレン単位又はセグメントの
数を示し、ｚは０又は１であり、ｘとｙとの和は０より
大きく、ｍはセグメントの数を示し、ｎは重合度を示す
ことを特徴とする電子的デバイス。1. An electronic device comprising polythiophene having the structural formula (I) of the following formula: In the formula, R and R ′ are side chains, A is a divalent bonding group, x and y represent the number of unsubstituted thienylene units or segments, z is 0 or 1, and x and y are An electronic device, wherein the sum is greater than 0, m indicates the number of segments, and n indicates the degree of polymerization.
て、Ｒ及びＲ’はそれぞれ独立して、アルキル及び置換
アルキルより選ばれ、Ａはアリーレンであることを特徴
とする電子的デバイス。2. The electronic device according to claim 1, wherein R and R ′ are each independently selected from alkyl and substituted alkyl, and A is arylene.
て、Ｒ及びＲ’はそれぞれ独立して、アルキルとアルキ
ル誘導体とから成る群より選ばれるものであって、前記
アルキル誘導体は、アルコキシアルキル、シロキシ置換
アルキル、パーフルオロアルキルであるパーハロアルキ
ル、及びポリエーテルであり、Ａは、フェニレン、ビフ
ェニレン、フェナントレニレン、ジヒドロフェナントレ
ニレン、フルオレニレン、オリゴアリーレン、メチレ
ン、ポリメチレン、ジアルキルメチレン、ジオキシアル
キレン、ジオキシアリーレン、及びオリゴエチレンオキ
シドである、アリーレンから成る群より選ばれることを
特徴とする電子的デバイス。3. The electronic device according to claim 1, wherein R and R ′ are each independently selected from the group consisting of alkyl and alkyl derivatives, and the alkyl derivative is alkoxy. Alkyl, siloxy substituted alkyl, perhaloalkyl which is a perfluoroalkyl, and polyether, A is phenylene, biphenylene, phenanthrenylene, dihydrophenanthrenylene, fluorenylene, oligoarylene, methylene, polymethylene, dialkylmethylene, An electronic device selected from the group consisting of arylene, which is dioxyalkylene, dioxyarylene, and oligoethylene oxide.
て、Ａは、炭素数約６〜約４０のアリーレンであること
を特徴とする電子的デバイス。4. The electronic device according to claim 1, wherein A is arylene having about 6 to about 40 carbon atoms.
て、ｎは約７〜約５，０００であり、いずれもポリスチ
レン標準を用いたゲル浸透クロマトグラフ法より求め
た、ポリチオフェンの数平均分子量（Ｍn）は約２，０
００〜約１０万であり、重量平均分子量（Ｍw）は約
４，０００〜約５０万であることを特徴とする電子的デ
バイス。5. The electronic device according to claim 1, wherein n is about 7 to about 5,000, and each has a number average of polythiophene determined by gel permeation chromatography using a polystyrene standard. The molecular weight (M n ) is about 2,0
An electronic device having a weight average molecular weight ( Mw ) of about 4,000 to about 500,000.
ート電極と、ゲート誘電体層と、ソース電極及びドレイ
ン電極と、前記ソース及びドレイン電極と前記ゲート誘
電体層とに接した半導体層と、を含み、前記半導体層は
請求項１に記載のポリチオフェンを含むことを特徴とす
る薄膜トランジスタ。6. A thin film transistor, comprising a substrate, a gate electrode, a gate dielectric layer, a source electrode and a drain electrode, and a semiconductor layer in contact with the source and drain electrodes and the gate dielectric layer. A thin film transistor, comprising: the semiconductor layer comprising the polythiophene according to claim 1.
構造式（１）〜（１４）を持つポリチオフェン類から成
る群より選ばれるポリチオフェンを含むことを特徴とす
る薄膜トランジスタ。 【化２】 7. A thin film transistor, comprising a polythiophene selected from the group consisting of polythiophenes having structural formulas (1) to (14) shown below. [Chemical 2]
って、式中、ｎは約５〜約５，０００であることを特徴
とする薄膜トランジスタ。8. The thin film transistor according to claim 7, wherein n is from about 5 to about 5,000.
あって、式中、ｘ、ｙ、及びｍは１〜３であり、ｚは０
又は１であり、前記電子的デバイスは薄膜トランジスタ
であることを特徴とする電子的デバイス。9. The electronic device according to claim 1, wherein x, y, and m are 1 to 3 and z is 0.
Or 1, and the electronic device is a thin film transistor.
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|---|---|---|---|
| US10/042,356 | 2002-01-11 | ||
| US10/042,356 US6621099B2 (en) | 2002-01-11 | 2002-01-11 | Polythiophenes and devices thereof |
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|---|---|
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| JP2003264327A5 JP2003264327A5 (en) | 2006-02-23 |
| JP4530616B2 JP4530616B2 (en) | 2010-08-25 |
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|---|---|---|---|
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|---|---|
| US (1) | US6621099B2 (en) |
| EP (1) | EP1329474B1 (en) |
| JP (1) | JP4530616B2 (en) |
| DE (1) | DE60308738T2 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| US6621099B2 (en) | 2003-09-16 |
| DE60308738D1 (en) | 2006-11-16 |
| DE60308738T2 (en) | 2007-01-18 |
| JP4530616B2 (en) | 2010-08-25 |
| EP1329474A1 (en) | 2003-07-23 |
| EP1329474B1 (en) | 2006-10-04 |
| US20030136958A1 (en) | 2003-07-24 |
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